BRPI1007696B1 - antifouling coating composition, antifouling treatment method, antifouling coating film and coated object - Google Patents

Abstract

antifouling coating composition, antifouling treatment method, antifouling coating film and coated object The present invention provides an antifouling coating material that can be used to form an excellent performance antifouling coating film antifouling and long-term physical properties and which excels in long term storage stability. The present invention provides an antifouling coating composition containing a copolymer [a] obtained by copolymerizing a monomer represented by the general formula (1) (wherein x represents acryloxy, methacryloyloxy, crotonoyloxy or isocrotonoyloxy, r1 represents a hydrogen atom). or methyl and r2 represents an alkyl group containing from one to six carbons) and a polymerizable monomer represented by the general formula (2) (wherein r3 represents a hydrogen or methyl atom, r4 represents an alkyl group containing from one to ten carbons, or an alkyl group containing from two to five carbons, to which an alkoxy group containing from one to four carbons is attached).

Description

(54) Title: COMPOSITION OF ANTI-SCALING COATING, ANTI-SCALING TREATMENT METHOD, ANTI-SCALING COATING FILM AND COATED OBJECT (73) Holder: NITTO KASEI CO., LTD .. Address: 17-14, NISHIAWAJI 3-CHOME, HIGASHIYODOGAWA-KU, OSAKASHI, OSAKA 5330031, JAPAN (JP) (72) Inventor: HITOSHI KITAMURA; TAKA YOSHI FUJIMOTO; TSUYOSHI IWAMOTO; TAKUYA YASUI.

Validity Term: 20 (twenty) years from 06/01/2010, subject to legal conditions

Issued on: 12/11/2018

Digitally signed by:

Liane Elizabeth Caldeira Lage

Director of Patents, Computer Programs and Topographies of Integrated Circuits

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COMPOSITION OF ANTI-SCALING COATING, ANTI-SCALING TREATMENT METHOD, ANTI-SCALING COATING FILM AND COATED OBJECT

Field of the technique [0001] The present invention relates to an anti-fouling coating composition, an anti-fouling coating film formed by using the composition, an object coated with the coating film on its surface and a method of anti-fouling treatment by forming the coating film, in order to avoid, for a long period of time, the fixation of aquatic fouling organisms on objects used or existing in sea water, such as ships, fishing nets, buoys , coolant ducts of power installations.

Prior art [0002] Barnacles, sepulches, common mussels, Bugula neritina, ascidae, green algae, sea lettuce, silt and similar aquatic fouling organisms are known to attach to vessels (especially the bottom of vessels), fishing nets , accessories of fishing nets and similar fishing equipment, aqueducts of power installations and similar structures submerged in sea water, and this causes a decrease in the speed of vessels and water flow, resulting in losses in terms of economy and resources. Consequently, efforts have been made to solve the problem mentioned above by applying anti-fouling coating material to prevent the fixation of aquatic fouling organisms.

[0003] Among these materials, the material of

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2/43 hydrolyzable coating based on organic tin, anti-fouling coating material whose main components are tributyltin methacrylate copolymer and cuprous oxide, has been widely used. When the coating film formed from the coating material comes into contact with seawater, the resin located on the surface of the coating film comes into contact with seawater and then hydrolyzes to become if soluble in water and, at the same time, releases a chemical agent. This coating material is known as a self-polishing coating material and exhibits an excellent anti-fouling effect.

[0004] However, the hydrolyzable coating material based on organic tin can no longer be used because of concern about marine pollution by the tributyltin compound released by hydrolysis.

[0005] Therefore, several researches have been done to obtain an anti-fouling coating material to replace the organic tin compound.

[0006] For example, in Patent Document 1, an anti-fouling coating material is proposed which contains, as a component of the resin, a copolymer obtained by the polymerization of an alkoxycarbonylalkyl (meta) acrylate ester. Patent Document 1 describes that the antifouling coating material exhibits the antifouling effect by dissolving the copolymer without hydrolysis. However, solubility is insufficient because hydrolysis does not occur and, therefore, the long-lasting anti-fouling effect

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3/43 deadline is not enough.

[0007] Patent Document 2 discloses an antifouling coating material improved over that of Patent Document 1. The antifouling coating material includes a copolymer obtained by adding a polyoxyalkylene group to the copolymer of the Patent Document

1. Solubility is increased by the addition of a polyoxyalkylene group to the copolymer of Patent Document 1. However, the copolymer dissolves without hydrolysis just like that of Patent Document 1 and, therefore, there is a problem as it is difficult to control both long-term solubility of the resin as its physical properties (eg water resistance).

[0008] Patent Documents 3 to 6 disclose hydrolyzable coating materials the main component of which is a resin containing metal other than the organic tin compound mentioned above.

[0009] However, there is a problem as the rate of decrease of the coating film formed from this coating material changes easily depending on the environment (for example, air temperature, water temperature etc.) and, therefore, it is difficult to control.

[0010] In addition, Patent Documents 7 to 10 disclose hydrolyzable coating materials that do not contain the organic tin compound mentioned above and whose main component is a resin containing organosilyl group.

These coating materials exhibit excellent anti-fouling performance and are highly resistant to water in

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4/43 mar and, consequently, are widely used.

[0011] However, there is a problem as the water contained in the raw materials of the coating materials or generated during the production of the coating material easily causes the hydrolysis of the resin component during storage and, consequently, causes thickening, freezing, and of coating materials. The addition of a dehydrating agent has been proposed to solve the problem. However, although the dehydrating agent has some effect, it does not completely solve the problem and therefore there is still concern about thickening, freezing, and the like, in the case of long-term storage. In addition, when handling raw materials, care must be taken with water, which worsens work efficiency.

[0012] Consequently, it has been desired to develop a new antifouling coating material that can be used to form an excellent antifouling coating film in antifouling performance and long-term physical properties, and that is excellent in long-term storage stability. Previous art reference

Document in patent Document in Patent 1: : JP-B-Sho 63-6198 Document in Patent 2: : JP-A-2003 -119419 Document in Patent 3 JP-B-Hei 7 -64985 Document in Patent 4: : JP-A-Hei 4-80205 Document in Patent 5: : JP-A-Hei 4-80269 Document in Patent 6: : JP-A-Hei 4-80270

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Patent Document 7: International Publication No.

84 / pamphlet 02195

Document in Patent 8: EP1127902 Document in Patent 9: JP-A-Hei 7-102193 Document in Patent 10: : JP-A-Hei 10-30071

Summary of the invention

Problems to be solved by the inventions [0013] The present invention provides an anti-fouling coating material that can be used to form an anti-fouling coating film excellent in anti-fouling performance and long-term physical properties, and which is excellent in long-term storage stability.

Problem solving means [0014] The present inventors have done intense research to solve the problem mentioned above and have found that the composition containing a specific polymer can solve the mentioned problem in order to complete the present invention.

[0015] The present invention relates to the following anti-fouling coating composition, an anti-fouling coating film formed by using the composition, an object coated with the coating film on its surface and an anti-fouling treatment method - fouling by forming the coating film.

1. An antifouling coating composition containing a copolymer [A] obtained by copolymerizing a monomer represented by the general formula (1):

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6/43 x— (jlH-C — R ² (1)

R ¹ where: X represents acryloyloxy, methacryloyloxy, crotonoyloxy or isocrotonoyloxy, R ¹ represents a hydrogen or methyl atom and R ² represents an alkyl group containing from one to six carbons;

and a polymerizable monomer represented by the general formula (2)

R ³

where: R ³ represents a hydrogen or methyl atom, R ⁴ represents an alkyl group containing from one to ten carbons, or an alkyl group containing from two to five carbons, to which an alkoxy group containing from one to four carbons is attached.

2. The antifouling coating composition of item 1 above, where when R ² in the general formula (1) is an alkyl group containing one or two carbons, R ⁴ in the general formula (2) is a branched alkyl group that contains three to ten carbons.

3. The antifouling coating composition of item 2 above, where when R ² in the general formula (1) is an alkyl group containing one or two carbons, the polymerizable monomer (2) is an isobutyl acrylate or methacrylate of isobutyl.

4. The antifouling coating composition of item 1 above, where when R ² in the general formula (1) is an alkyl group containing three to six carbons, the alkyl group is a branched alkyl group.

5. The antifouling coating composition of any of items 1 to 4 above, wherein the amount of use of the monomer (1) is 10 to 80% by weight relative to the total weight of the monomers.

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6. The antifouling coating composition of any of items 1 to 5 above, wherein the amount of use of the monomer (2) is 20 to 90% by weight relative to the total weight of the monomers.

7. The antifouling coating composition of any of items 1 to 6 above, which also contains an antifouling [B].

8. The antifouling coating composition of item 7 above, wherein the antifouling [B] is a cuprous oxide.

9. The antifouling coating composition of any of items 1 to 8 above, which also contains a release modifier [C].

10. The antifouling coating composition of item 9 above, wherein the release modifier [C] is at least one member selected from the group consisting of pitch, derived from pitch and salt from pitch metal.

11. The anti-fouling coating composition of any of items 1 to 10 above, which still contains a plasticizer [D].

12. An antifouling treatment method comprising the step of forming an antifouling coating film on the surface of an object to be coated using the antifouling coating composition of any of items 1 to 11 above.

13. An antifouling coating film formed by using the antifouling coating composition reported in any of items 1 to 11 above.

14. A coated object that contains the anti-fouling coating film of item 13 above on its surface. Effect of the invention [0016] The coating composition

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8/43 antifouling of the present invention has excellent long-term storage capacity. Consequently, the composition of the present invention does not become thick, frozen or solidified, even after long-term storage.

[0017] The antifouling coating film formed by using the antifouling coating composition of the present invention has adequate solubility. Therefore, the coated object that contains the coating film on its surface can maintain anti-fouling performance for a long time. Particularly, when the antifouling coating film of the present invention is formed on the bottom of a ship, aquatic fouling organisms are unlikely to stick or accumulate, even during anchoring, rigging or when the ships are stationary, and therefore , the long-term anti-fouling effect is displayed. This reduces the frictional resistance of ships and the cost of fuel during navigation.

[0018] Furthermore, the anti-fouling coating film on the surface is basically free from defects in the coating film, even after a long period of time. For this reason, after using the coated object for a predetermined period, it is desirably possible to form a new antifouling coating film by means of new direct coating of the antifouling coating film composition on the object. This makes it possible to continuously maintain the anti-fouling effect simply and cheaply.

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Conduct of the invention [0019] In the following, the present invention will be explained in detail.

Anti-fouling Coating Composition [0020] The anti-fouling coating composition of the present invention contains a copolymer [A] obtained by copolymerizing a monomer (hereinafter also referred to as monomer (1)), represented by the general formula (D:

íl ₂

X — CjJH-C — R ² (1

R ¹ where: X represents acryloyloxy, methacryloyloxy, crotonoyloxy or isocrotonoyloxy, R ¹ represents a hydrogen or methyl atom and R ² represents an alkyl group containing from one to six carbons;

and a polymerizable monomer (hereinafter also referred to as monomer (2)), represented by the general formula (2):

(2) where: R ³ represents a hydrogen or methyl atom, R ⁴ represents an alkyl group containing from one to ten carbons, or an alkyl group containing from two to five carbons, to which an alkoxy group containing from one to four carbons is attached.

<Copolymer [A]>

[0021] Just like coating films

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10/43 mentioned above containing resin based on organic tin or resin based on organosilyl group, the coating film containing copolymer [A] allows the copolymer [A] to be hydrolyzed and released into seawater and thus the coating film is renewed while exhibiting a self-polishing effect and releases the antifouling in the coating film. As a result, the coating film formed by using the composition of the present invention can exhibit anti-fouling performance.

[0022] Copolymer [A] is formed by the copolymerization of monomer (1) and monomer (2). The monomer (1) has the structure below. ₀

--- C - O - CH — C - OR ¹ [0023] The structure mentioned above includes an ester bond that provides adequate hydrolysis capacity. Therefore, the polymer obtained by the polymerization of the monomer (1), which has the structure mentioned above, is hydrolyzed at an appropriate speed in seawater and gradually dissolves in it, thus exhibiting excellent long-term anti-fouling performance.

[0024] Under acidic to neutral conditions, the hydrolysis rate of the monomer (1) is less than that of a (meta) acrylate containing organosilyl group or a similar monomer, but in an alkaline condition that is more alkaline than an alkaline condition weak (pH 8 to 9), the hydrolysis rate of monomer (1) is close to that of an organosilyl (meta) acrylate.

[0025] This characteristic nature of the monomer (1)

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11/43 exists in the polymer obtained by polymerizing the monomer. As the polymer has a lower hydrolysis capacity than that of organosilyl (meta) acrylate, or similar, under acidic to neutral conditions, the polymer is more difficult to hydrolyze when water is mixed during production or storage. anti-fouling coating material. Therefore, the coating composition containing the polymer mentioned above exhibits high storage stability, even when a water removal component is not present. This contrasts with the coating composition using an (meth) acrylate containing organosilyl group, or similar, which requires a component for removing water (dehydrating agents etc.) to improve storage stability.

[0026] Consequently, the polymer mentioned above exhibits an adequate hydrolysis rate in seawater, which is in an alkaline condition that is more alkaline than the weak alkaline condition (pH 8 to 9), and thus the coating can be renewed for a long period. As this polymer is hydrolyzable, the solubility of the coating film is therefore stable over a long period. Therefore, the anti-fouling performance and the proper condition of the coating film due to the stable renovation can be maintained for a long period.

[0027] However, the polymer containing the monomer (1) tends to have low solubility in a common solvent for a coating material, such as aromatic solvent, ester-based solvent, ketone-based solvent, or the like.

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12/43 [0028] In particular, the polymer tends to have lower solubility in xylene, which is a solvent more commonly used for an antifouling coating composition than an ester-based solvent and a ketone-based solvent.

[0029] Consequently, in order to improve the solubility of the polymer containing the omomer (1) in a solvent, the copolymer [A] includes, as an essential component, a polymerizable monomer different from the monomer (1), represented by the general formula (2 ):

R ³

where: R ³ represents a hydrogen or methyl atom, R ⁴ represents an alkyl group containing from one to ten carbons, or an alkyl group containing from two to five carbons, to which an alkoxy group containing from one to four carbons is attached.

[0030] When a monomer other than monomer (2) is used as a monomer to copolymerize with the monomer (1), the copolymer obtained is difficult to exhibit long-term anti-fouling performance while achieving a sufficient level of solubility in a solvent , solubility of the coating film and coating film property.

[0031] For example, when styrene, which is one of the general purpose polymerizable monomers, is used as a polymerizable monomer, the copolymer obtained has better solubility in a solvent than the polymer obtained from the monomer (1) only. However, the coating film formed

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13/43 from the coating composition containing the copolymer has problems nonetheless, so the coating film has low solubility, tends to cause cracking, or the like, and therefore is difficult to exhibit long-lasting anti-fouling performance term.

[0032] Furthermore, the polymer obtained by using other common polymerizable monomers is difficult to exhibit long term anti-fouling performance while achieving a sufficient level of solubility in a solvent, solubility of the coating film and property of the coating film. Therefore, monomer (2) is used as a component of the copolymerization monomer of copolymer [A], in order to solve the problem mentioned above and exhibit long-term anti-fouling performance.

[0033] The monomer (1) is now explained in detail.

[0034] X in the general formula (I) represents acryloyloxy, methacryloyloxy, crotonoyloxy or isocrotonoyloxy.

[0035] In particular, it is preferable that X in the general formula (I) is acryloyloxy, in view of the solubility of the coating film.

[0036] R ¹ in the general formula (I) represents a hydrogen or methyl atom. The rate of hydrolysis tends to be faster when R ¹ is a hydrogen atom than when R ¹ is methyl. Therefore, it is preferable that R ¹ is a hydrogen atom, in view of the hydrolysis capacity.

[0037] R ² in the general formula (I) represents an alkyl group containing from one to six carbons.

[0038] As the number of R ² carbons in the

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14/43 monomer (1) increases, the solubility of the copolymer in a solvent increases. However, when the carbon chain is very long, the hardness of the coating film deteriorates.

This can result in deterioration of the coating film's property, such as bubble generation, similar cold flow.

Therefore, in view of the solubility of the copolymer in a solvent and the property of the coating film, R ² in the monomer (1) uses an alkyl group that contains from one to six carbons.

[0039] Examples of the alkyl group containing from one to six carbons represented by R ² in the general formula (1) include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, 2 -methylbutyl,

1.2- dimethylpropyl, n-hexyl, 1-ethylbutyl, 2-ethylbutyl,

1.2- dimethylbutyl.

[0040] In this invention, when the carbon number of R ² is as low as 1 or 2, compatibility with a solvent tends to be low. In order to improve this, when R ² is methyl or ethyl, it is preferable to use a copolymerization monomer (2) whose R ⁴ in the general formula (2) is a branched alkyl group containing from three to ten carbons.

[0041] When the number of carbons in the alkyl group represented by R ² in the general formula (1) is three to six, it is preferable that the alkyl group is a branched alkyl group.

The solubility of the polymer in a solvent is better when R ² is a branched alkyl group than when R ² is an unbranched alkyl group; therefore, solubility in a solvent, particularly in a solvent containing xylene in an amount

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15/43 from 70 to 100%, increases and the property of the coating film, as resistance of the coating film, increases.

[0042] The amount of use of the monomer (1) is preferably 10 to 80% by weight, and more preferably 20 to 60% by weight, in relation to the total weight of the monomers, with a view to improving the compatibility of the copolymer [A] with a solvent or the like, the appropriate hydrolysis capacity of the coating film, the suitable properties of the coating film, or the like.

[0043] In the present invention, the preferred examples of monomer (1) are as follows.

O

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[0044] For ο monomer (1), one member can be used alone or two or more members can be used in combination. When two or more members of the monomers (1) are used in combination, the solubility of the coating film and the properties of the other coating film can be adjusted more appropriately.

Production of Monomer (1) [0045] Monomer (1) can be produced, for example, from α-halocetone and an unsaturated carboxylic acid or the acid metal salt. Specific production methods include a reaction method between an aqueous solution of the alkali metal salt of an unsaturated carboxylic acid, such as sodium methacrylate salt prepared from methyl methacrylate, and α-halocetone (ketone whose carbonyl group is replaced by a halogen element in the α position), such as chloroacetone (U.S. Patent No. 2376033), and a reaction method, in the presence of triethylamine, between an unsaturated carboxylic acid, such as methacrylic acid, and a-haloketone, such as chloroacetone ( Journal of Polymer Science: Part A: Polymer Chemistry, Vol. 26 2295-2303 (1988)).

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17/43 [0046] The monomer (2) is explained in more detail.

[0047] R ³ in the general formula (2) represents a hydrogen or methyl atom.

[0048] Examples of the alkyl group containing from one to ten carbons represented by R ⁴ in the general formula (2) include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, hexyl , cyclohexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decila. Examples of the alkyl group containing two to five carbons for which an alkoxy group containing one to four carbons include 2-methoxyethyl, 2-ethoxyethyl, 3-methoxypropyl,

3-ethoxypropyl, 4-methoxybutyl.

[0049] Examples of the monomer (2) include goal) acrylate of methyl, (meta) ethyl acrylate, goal) acrylate in n-propyl, (meta) acrylate isopropyl, goal) acrylate in n-butyl, (meta) acrylate isobutyl, goal) acrylate in pentila, (meta) acrylate of isopentyl, goal) acrylate in n-hexyl, (meta) cyclohexyl acrylate, goal) acrylate in n-octyl, ( meta) acrylate 2-ethylhexyl, goal) acrylate in n-nonila, ( meta) acrylate 2-methoxyethyl, goal) acrylate of 2-ethoxyethyl, ) acrylate

meta) 4-methoxybutyl acrylate.

3-methoxypropyl, [0050]

In this invention, when R ² is an alkyl group containing one or two carbons, it is preferable to use the monomer whose R ⁴ is branched alkyl.

Just as the monomer (2), whose R ⁴ is branched alkyl, isobutyl acrylate or isobutyl methacrylate is preferable. When the R ² of the monomer (1) is an alkyl group containing one or two carbons, the

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18/43 solubility in xylene, or in a similar aromatic solvent, tends to be low. By the use of the monomer (2), whose R ⁴ has a branched structure, the solubility in a solvent, particularly in a solvent containing xylene in an amount of 70 to 100%, is effectively increased.

[0051] The monomer (2), as needed, can be used alone or in combination. When two or more members are combined, compatibility with a solvent, or the like, and the property of the coating film can be adjusted more appropriately.

[0052] The amount of use of the monomer (2) is preferably from 20 to 90% by weight, and more preferably from 30 to 70% by weight, in relation to the total weight of the monomers, with a view to improving the compatibility of the copolymer [A] with a solvent or the like, the proper hydrolysis capacity of the coating film, the suitable properties of the coating film, or the like.

[0053] As components of the monomer of copolymer [A], another monomer (3), different from monomer (1) and monomer (2), can be used.

[0054] Examples of the other monomer (3) include phenyl (meta) acrylate, tolyl (meta) acrylate, xylyl (meta) acrylate and similar aryl (meta) acrylate monomers; benzyl (meta) acrylate, phenethyl (meta) acrylate and similar aralkyl (meta) acrylate monomers; styrene, α-methyl styrene, vinyl toluene and similar vinyl group aromatic monomers; dimethyl malate, diethyl malate and maleic acid diester monomers

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19/43 similar; (meta) 2-hydroxyethyl acrylate, (meta) acrylate

2-hydroxypropyl, (meta) 3-hydroxypropyl acrylate, (meta) 3-hydroxybutyl acrylate, (meta) acrylate

4-hydroxybutyl and similar hydroxyalkyl (meta) acrylate monomers; (meta) 2-aminoethyl acrylate, (meta) 3-aminopropyl acrylate, (meta) acrylate

2-N, N-dimethylaminoethyl, (meta) acrylate

2- N, N-diethylaminoethyl, (meta) acrylate

3- N, N-dimethylaminopropyl, (meta) acrylate

3-N, N-diethylaminopropyl and alkyl (meta) acrylate monomers containing similar amino groups; N- (2-aminoethyl) (meta) acrylamide, N- (3-aminopropyl) (meta) acrylamide, N- [2- (dimethylamino) ethyl] (meta) acrylamide, N- [meta) acrylamide 3- (dimethylamino) propyl] and similar (meta) acrylamide based monomers; vinyl acetate, vinyl benzoate and similar vinyl ester monomers; (meta) trialkylsilyl acrylate and various types of similar monomers each containing a silyl ester group.

[0055] When the monomer (3) is used, the amount of use of the monomer (3) is preferably 0.5 to 40% by weight, and more preferably 1 to 20% by weight, in relation to the total weight of the monomers.

[0056] The average molecular weight (Mw) of the copolymer [A] is preferably from 1,500 to 200,000, and more preferably from 5,000 to 100,000.

[0057] The production method of the copolymer [A] of the present invention is not particularly limited, but an example is a method of mixing the monomer (1) and monomer (2) and the

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polymerization gives mixture in presence of a initiator of polymerization in around 60 to 180 ° C. [0058] Examples of initiator of polymerization

mentioned above include similar benzoyl peroxide, t-butyl peroxybenzoate and similar peroxide based radical polymerization initiators, azobisisobutyronitrile and similar azo based radical polymerization initiators. These polymerization initiators can be used alone or in combination.

[0059] Examples of the polymerization method for producing the copolymer [A] include solution polymerization, suspension polymerization, emulsion polymerization and the like. Among these, solution polymerization using a common organic solvent is preferable because of its versatility.

[0060] Examples of the solvent used for the solution polymerization mentioned above include toluene, xylene and solvents based on similar aromatic hydrocarbons; n-butyl acetate and similar ester-based solvents; methyl isobutyl ketone and similar ketone-based solvents. As a solvent, xylene is particularly preferable because of its versatility as a solvent for an antifouling coating composition. These solvents can be used alone or in combination.

[0061] The amount of copolymer [A] in the antifouling coating composition of the present invention is not limited, but is generally 3 to 50% by weight, and preferably 5 to 30% by weight, based on the content of

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21/43 solids of the antifouling coating composition.

[0062] The antifouling coating composition of the present invention may further contain, if

necessary, an antifouling [B] , a modifier of release [C], one plasticizer [D] and the like, beyond copolymer [A]. Addition can enhance the It is made anti-fouling. <Anti-fouling [B]> [0063] The antifouling [B] can be any

substance, provided it has a deadly or repellent effect against aquatic fouling organisms. Examples of the antifouling [B] include cuprous oxide, copper rhodide, copper powder, copper 2-mercaptopiridine-N-oxide and similar copper compounds; Zinc 2-mercaptopiridine-N-oxide, zinc bis (dimethyldithiocarbamoyl), ethylenebis (dithiocarbamate), zinc dimethyldithiocarbamate and similar zinc compounds; 2,4,5,6-tetrachloroisophthalonitrile,

3.4- dichlorophenyl-dimethylurea,

4.5- dichloro-2-N-octyl-3- (2H) -isothiazoline, N, N-dimethyl-N'-phenyl- (N-fluorodichloromethylthio) sulfamide, tetramethylthiuram disulfide, tetraethylthiuram disulfide, 3-iodo-2- propynyl butylcarbamate, pyridine-triphenylborane, 2- (methoxycarbonylamino) -benzimidazole and similar metal-free compounds. These antifouling can be used alone or in combination. Particularly, as an antifouling [B], cuprous oxide is preferable because it provides an excellent antifouling effect.

[0064] The amount of antifouling [B] in the

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The composition of the present invention is not particularly limited, but is generally from 0.1 to 75% by weight, and preferably from 1 to 60% by weight, based on the solids content of the composition of the present invention. When the amount of antifouling [B] is less than 0.1% by weight, a sufficient antifouling effect may not be obtained. When the amount of antifouling [B] is greater than 75% by weight, the coating film obtained is fragile and the adhesion of the coating film to the coated object is poor; therefore, the coating film does not sufficiently exhibit the function as an anti-fouling coating film.

<Release Modifier [C]>

[0065] Examples of the release modifier [C] include pitch, derived from pitch and salt of pitch metal, or a monocarboxylic acid and a salt of the acid, and the like.

[0066] Examples of pitch include tall oil pitch, gum pitch, wood pitch, and the like. Examples of the pitch derivative include hydrogenated pitch, maleised pitch, formylated pitch, polymerized pitch, and the like. For the pitch metal salt and pitch metal salt, the product obtained by the reaction of a metal compound with pitch can be used. Examples of the metal salt include pitch zinc salt, calcium pitch salt, copper pitch salt, pitch magnesium salt, and the like.

[0067] Examples of monocarboxylic acid include fatty acid, synthetic fatty acid, naphthenic acid, and the like, each having 5 to 30 carbons. Examples of the monocarboxylic acid salt include copper salt, zinc salts, salt of

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23/43 magnesium, calcium salt, and the like.

[0068] In particular, the composition of the present invention preferably includes, as a release modifier [C], at least one member selected from the group consisting of pitch, derived from pitch and salt of pitch metal, in which a suitable release property is given to the composition of the present invention.

[0069] The amount of the release modifier [C] in the composition of the present invention is generally 1 to 80 parts by weight, preferably 10 to 50 parts by weight, relative to 100 parts by weight of the copolymer [A]. When the release modifier [C] is less than one part by weight, the effect of avoiding the fixation of aquatic fouling organisms, particularly during rigging, cannot be expected. When the amount of the release modifier [C] is greater than 80 parts by weight, defects such as cracking, peeling and the like tend to occur and, therefore, the effect of avoiding the fixation of aquatic fouling organisms may not be sufficiently exhibited.

<Plasticizer [D]>

[0070] By adding the plasticizer [D] to the antifouling coating composition of the present invention, it is possible to improve the plasticity of the compound and, as a result, it is possible to form a suitably strong coating film.

[0071] Examples of the plasticizer [D] include tricresyl phosphate, trioctyl phosphate, dioctyl phthalate, chlorinated paraffin, liquid paraffin, ethyl vinyl ether polymer,

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24/43 polybutene, and the like. These plasticizers can be used alone or in combination.

[0072] The amount of plasticizer [D] in the composition of the present invention is generally 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, relative to 100 parts by weight of the copolymer [A] .

<Other Additives>

[0073] In addition, the antifouling coating composition of the present invention, if necessary, may include a pigment, a dye, an antifoaming agent, an anti-slip agent, a dispersant, an anti-settling agent, a dehydrating agent, an organic solvent , and the like.

[0074] Examples of the pigment include zinc oxide, red iron oxide, talc, titanium oxide, silica, calcium carbonate, barium sulfate, oxidizing calcium, oxidizing magnesium, and the like. These pigments can be used alone or in combination.

[0075] Examples of dye include various types of organic dyes soluble in an organic solvent.

[0076] Examples of the antifoam agent include an antifoam agent based on silicone resin, an antifoam agent based on acrylic resin, and the like.

[0077] Examples of the anti-slip agent, dispersant or anti-sedimentation agent include fatty acid amide wax, oxidized polyethylene, and the like.

[0078] In the coating composition of the present invention, a dehydrating agent to prevent hydrolysis does not

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25/43 is necessary because the copolymer [A] mentioned above has high stability in relation to water. However, a dehydrating agent can be used to remove excess water in the coating material.

[0079] Examples of the dehydrating agent include anhydrous plaster, adsorbent based on synthetic zeolite, orthoesters, tetraethoxysilane and similar silicates, and isocyanates. These dehydrating agents can be used alone or in combination.

[0080] Examples of the organic solvent include aliphatic solvent, aromatic solvent, ketone-based solvent, ester-based solvent, ether-based solvent, and similar solvent commonly used in antifouling coating material. These solvents can be used alone or in combination.

Production Method of the Anti-Fouling Coating Composition [0081] The anti-fouling coating composition of the invention can be produced, for example, by mixing and dispersing a mixed solution containing copolymer [A] and the like using a dispersant.

[0082] The amounts of copolymer [A] and the like can be adjusted accordingly so that the resulting antifouling coating composition contains copolymer [A] and the like as described above.

[0083] The mixed solution is preferably obtained by dissolving or dispersing various materials, as well as the copolymer [A] in a solvent. As a solvent, the solvent

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26/43 organic mentioned above can be used.

[0084] For the dispersant, for example, one can properly use one that can be used as a micro spray. For example, a commercially available homo-mixer, sand mill, ball mill, or the like can be used. In addition, the mixed solution can be mixed and dispersed using a container with an agitator, to which glass beads are added for mixing and dispersing.

Anti-fouling Treatment Method, Anti-fouling Coating Film and Coated Object [0085] The anti-fouling treatment method of the invention is characterized by the formation of an anti-fouling coating film on the surface of the object to be coated, using if the antifouling coating composition explained above. The antifouling treatment method of the present invention can prevent the adhesion of aquatic fouling organisms by gradually dissolving the surface of the antifouling coating film, in order to continually renew the surface of the coating film. After the coating film has dissolved, the anti-fouling effect can be continuously exhibited by re-coating the composition.

[0086] Examples of objects on which a coating film can be formed include ships (particularly ship bottoms), fishing equipment, structures submerged in sea water, etc. Examples of fishing equipment include fishing nets for use in

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27/43 aquaculture or in fixed nets and accessories of fishing nets, such as buoys attached to fishing nets, ropes etc. Examples of structures submerged in seawater include power plant aqueducts, bridges, port facilities, etc.

[0087] The antifouling coating film of the present invention can be formed by applying the antifouling coating composition to the surface (in whole or in part) of the object on which a coating film is formed.

[0088] Examples of the coating method include brush coating, spray coating, dipping, flow coating, rotation coating etc. These methods can be used alone or in combination.

[0089] The coating composition is dried after application. The drying temperature can be room temperature. The drying time can be appropriately selected, depending on the thickness of the coating film, etc.

[0090] The thickness of the anti-fouling coating film can be appropriately selected, depending on the type of object on which a coating film is formed, the speed of navigation of the ship, the temperature of the sea water, etc. For example, when the object on which a coating film is formed is a ship bottom, the thickness of the anti-fouling coating film is generally 50 to 500 pm and, preferably, 100 to 400 μm.

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[0091] The coated object of the present invention has the anti-fouling coating film on its surface and may have the anti-fouling coating film on the whole or part of it.

[0092] The coated object of the present invention can exhibit the anti-fouling effect continuously. Therefore, it can be desirably applied to ships (particularly ship bottoms), fishing equipment, structures submerged in sea water, etc.

[0093] For example, when the antifouling coating film is formed on the surface of a ship bottom, the antifouling coating film gradually dissolves from the surface, so that the surface of the coating film it is always renewed. This prevents the adhesion of aquatic fouling organisms.

[0094] Furthermore, the hydrolysis rate of the anti-fouling coating film in seawater is desirably controlled. Therefore, ships benefit from the anti-fouling effect for a long period of time; in addition, even when ships are not moving, for example, during docking, rigging etc., adhesion and accumulation of aquatic fouling organisms are rarely observed and the anti-fouling effect is exhibited for a long time.

[0095] The surface of the anti-fouling coating film is basically free of cracking or peeling, even after a long period of time. Therefore, it is not necessary to completely remove the existing coating film before re-forming a new coating film.

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29/43 coating. In this way, by re-coating the surface with the composition of the anti-fouling coating film directly, the film can be effectively formed. This makes it possible to continuously maintain the anti-fouling effect easily and cheaply.

[0096] The characteristics of the invention will be further clarified with reference to the Examples, etc. shown below; however, the invention is not limited by the Examples. In the Examples, parts means parts by weight, unless otherwise specified. The molecular weight (Mw) is an average molecular weight determined by means of gel permeation chromatography (GPC) (using a polystyrene standard).

[0097] The GPC was carried out under the following conditions.

Equipment: HLC-8220 GPC; Tosoh Corporation

Column: TSK-gel Super HZM-M. two

Flow rate: 0.35 ml / min

Detector: RI

Column thermostat temperature: 40 ° C

Eluted: THF [0098] The non-volatile content is in% by weight of copolymer [A] after heating for one hour at 125 ° C, relative to the weight of copolymer [A] before heating.

Production Example 1 (Copolymer Production [A-1]) [0099] A solvent (xylene) (100 parts) was loaded into a reaction vessel equipped with a thermometer, reflux condenser, stirrer and drip funnel ; then, a mixture of a monomer shown in Table 1 (1-1) (45 parts), methyl methacrylate (2-1) (30 parts), acrylate

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30/43 of 2-methoxyethyl (2-4) (25 parts) and azobisisobutyronitrile polymerization initiator (1) (0.9 part) was added dropwise to the container, by stirring at 110 to 115 ° C in an atmosphere of nitrogen . After the addition in drops, azobisisobutyronitrile (2) (0.5 part) was added to the resulting reaction solution, and then the reaction was carried out for 4 hours at 110 ° C, with stirring, in order to obtain a copolymer [ TO 1]. Table 2 shows the average molecular weight (Mw) and the non-volatile content of [A-1].

Production Examples 2 to 17 (Production of Copolymers [A-2] to [A-17] [0100] By using a monomer shown in Table 1 and the following, a solvent shown in Table 2 and a polymerization initiator, a The polymerization reaction is carried out according to the same procedures as in Production Example 1, in order to obtain copolymers [A-2] to [A-17] .Table 2 shows the Mw and the non-volatile content.

2-1 ··· Methyl methacrylate

2-2 n-butyl acrylate

2-3 ••• isobutyl methacrylate

2-4 ··· 2-methoxyethyl acrylate

2- 5 ••• 2-methoxyethyl methacrylate

3- 1 ··· styrene

Table 1

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Monomero (1-1) O O Monomer (1-7) O Monomero (1-2) The ¹ Monomer (1-8) 0 0 ' Monomero (1-3) O O Monomer (1-9) 0 Monomero (1-4) O The 1 Monomer (1-10) O Monomero (1-5) O O Monomer (1-11) 0 Monomero (1-6) O Monomer (1-12) O

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O 2 Q iZL CO Q-3 The CD The d ^- 100 co o LD 0 ' The O C-J CD C-J CO co d- the E AND Φ o O CO CD d ^- C-J C-J 1 □ r The CD The d ^- the o co o LD o o o C-J C-J LlI = 1 Ό T " r-1 laughs co O Í cr O O O 1 Γ— Γ-- 1 í LTJ d- LTJ d- O O O co o LD 0 ' ood ^- CJ CJ CO cd d- CD CD 1 < The CD The d ^- O O co o LD ó ^- O O C-J d- C-J r- CD d- LO B 1 < The CD The d ^- O O co o LD ó ^- O C-J dog CO CD d- τ ± ΓΊ O O co LTJ O O O 1 í CD d- O O O Γ-C-J The bi CO CO 1 í LO d- LTJ d- O O O co o LD 0 ' the the d r-C-J Cp CD d- C-J C-J 1 í The CD The d- O O co o LD o O The CD CD C-J CO CD d ^- O O O co LT) O O CD í CD d- l_J O O CO C-J CD d ^- the ÍIU O 3 “O O O 1 í The CD CO O O O co o b o O O CO LT) C-J CO CD d ^- CL φ O CD CD 1 í The CD The d ^- O O co o LTj 0 ' O O CO b co cd d ^- O C-J Cl O CD AND CO CO 1 "l co LTJ O Ί ': c í CD d ^- O O O LD r— CD d LU C-J Γ- r— 1 í Ü | d- bd ^- O O O CO o LD ó ^- o o CD C-J r-cd d- CD CD | —I I ^- 1 1 "l CD LTJ the o r-- í CD d ^- l_l O O d C-J co U j d- LO LT) | —1 O 1 "l CD LTJ the o CO í CD d- l_l O O the coconut U j d- d ^- d- 1 í the CD CO O O O ro LD 0 ' o o C-J dogs CO CD d- CO co O O O O r— LT) the o C-J i CO d- co l_l O' O' LD LD C-J The LD C-J C-J O LO LO O r— LT) O O O i τ ± co C-J l_J O O CD C-J l_J LD - 1 í LO T ± CO LO C-J O O CD o LD 0 ' OO d ^- CJ CJ cq CD d- ._____. i M iTl Φ o h ^- H -------1 Φ U OO c ^-:: ιΌ - T— C-J CO d- B CD r— CO CD O C-J I C-J co d ^- LO T- 3 _ü O _ o Φ -gj X ΜΊ 'φ -φ AND -3 Ç> o -Ξ: Cl o 1 1 1 C-J C-J C-J C-J C-J CO The Γ s ΐ ΨΊ ΜΊ 1d c o iü U _φ Φ φ u N 3 L · O O Cl O > ΓΊ -K- z u = L _Ü + rS

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Examples 1 to 18 (Production of Coating Compositions) [0101] As well as copolymer [A], copolymers [A-1] to [A-17] obtained in Production Examples 1 to 17 were added to the containers in proportion ( % by weight) shown in Table 3. As well as the antifouling [B], the release modifier [C], the plasticizer [D], the pigment, the anti-slip agent and the solvent, the antifouling, the modifier of release, the plasticizer, the pigment, the anti-slip agent and the solvent shown in Table 3 were added to the container in the proportion (% by weight) shown in Table 3; then, glass beads with a diameter of 1.5 to 2.5 mm were added for mixing and dispersing, and the resulting mixture was agitated, mixed and dispersed by using the stirrer of the experiment, in order to prepare a composition of the film of coating. In Table 3, cuprous oxide has the trade name NC-301, manufactured by Nissin Chemco, Ltd .; polyvinyl ether has the trade name Lutonal A-25, manufactured by BASF; and A630-20X has the trade name Dispalon A630-20X, manufactured by Kusumoto Chemicals, Ltd. The release modifier [C] is a solution obtained by dissolving gum pitch in the same solvent used for the production of copolymer [A] ( the amount of gum pitch in the solution is 50% by weight).

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Q. And u LU r - j i CM LO co You LO 00 O CM in M- Γ-- Ü? O o i CM LO Ú- co - LO 00 O CM in Μ r-- Γ-- · the o LU 22 CM LO Ú- co '7? - LO 00 O CM in Μ r-- Γ-- · the o Γ-- CM LO co Tj - LO 00 O CM in M- Γ-r-- ' the o co CM LO co '7? - LO 00 O CM in Μ r-r-- ' the o LO CM LO co '7? - LO 00 O CM go> Μ Γ-r-- ' the o d- CM LO co 7l · - LO 00 O CM m_ M- r-r-- ' the o 22 CM LO d- co Tj - LO 00 O CM in M- r-Γ-- · the o cm CM LO Ú- co Tj - LO 00 O CM in M- r-- Γ-- · the o - CM LO Ú- co Tj CM LO 00 O CM in M- r-- CD the o O CM LO Ú- co Tj - LO 00 O CM in M- r-- Γ-- · the o You CM LO Ú- co Tj - LO 00 O CM in M- r-- Γ-- · the o 00 CM LO Ú- co Tj - LO 00 O CM in M- r-- Γ-- · the o Γ-- CM LO Ú- co Tj - LO 00 O CM in M- r-- Γ-- · the o CO CM LO Ú- co Tj - LO 00 O CM in M- r-- Γ-- · the o LO CM LO Ú- co Tj - LO 00 O CM in M- r-- Γ-- · the o CM LO Ú- co Tj - LO 00 O CM LQ M- Γ-- Γ-- · the o 00 CD LO Ú- co 7l · - LO 00 o CM LO M- Γ-Γ-- · the o CM cm LO Ú- co Τΐ YOU And the Ü5 Φ ΤΊ z «l · ω · Ι · The c · c r-.J Φ ΤΊ m ω - LO 00 O CM in Μ r-- Γ-- · the o - CD LO co Tj - LO 00 O CM it M- Γ-í <. · the o Table 3 í CM 00 í M- í IO i CO í Γ-- í 00 · i T. i O í CM i 22 í í LO CO i í CM □ r co cr O Ui o ü. = 1 u o TZJ O Φ □ Ξ □ u σ 'n AND □ there □ the c ixi σ 'n and □ there O 1 = l7> 5 £ υ Ξ TI sü O Μ Y y r · LL. = E IT o> U Cl Φ Ε ο C5 · Ι · = 1 · 1 · ω J2 Έ O LL Φ Ό Φ LL1 TI σ 2 o u YOU ç 2 ΐ Cl O O c ΓΜ Φ Ό The TZJ Ci the 'c l · - Φ Ό the TZJ Cl Ü O TJ 1- r φ AND φ> ü φ Ll φ Ό Ü Ç O CM cò CO < ü and _φ X • n ç O φ U zi -Q The _Ui Φ 2 o 1— □ Φ AND " iZl □ u φ ç 2 ui ion _c ç < · Ι · ’U S o 7 O .2 · υ H □ Φ and Ui τι Cl O ç Φ AND Di Ü_ O φ Φ ^s 5 = Oi 'ΐ - <° O Ui Φ Φ and Φ Ξ- 0 ω

Comparative Production Example 1 (Copolymer Production [Q-1]) [0102] A solvent (xylene) (100 parts) was loaded into a reaction vessel equipped with a thermometer, reflux condenser, stirrer and funnel. drip;

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35/43 then, a mixture of a monomer shown in Table 1 (1-1) (100 parts) and an azobisisobutyronitrile polymerization initiator (1) (0.8 part) was added dropwise to the container, with stirring at 110 at 115 ° C in a nitrogen atmosphere. Shortly after the addition in drops, the reaction solution started to become cloudy and a viscous material, which appeared to be a polymer, became attached to the container and, therefore, it was not possible to obtain a uniform polymer solution.

Comparative Production Example 2 (Copolymer Production [Q-2]) [0103] A solvent (xylene) (100 parts) was loaded into a reaction vessel equipped with a thermometer, reflux condenser, stirrer and funnel. drip; then, a mixture of a monomer shown in Table 1 (1-6) (60 parts), styrene (3-1) (40 parts) and azobisisobutyronitrile polymerization initiator (1) (0.8 part) was added in drops to the container by stirring at 110 to 115 ° C in a nitrogen atmosphere. After the addition in drops, azobisisobutyronitrile (2) (0.5 part) was added to the resulting reaction solution, and then the reaction was carried out for 4 hours at 110 ° C, with stirring, in order to obtain a comparative copolymer [ Q-2]. Table 2 shows the average molecular weight (Mw) and the non-volatile content of [Q-2].

Comparative Production Example 3 (Copolymer Production [Q-3]) [0104] A solvent (xylene) (100 parts) was loaded into a reaction vessel equipped with a thermometer, reflux condenser, stirrer and funnel. drip; then, a mixture of a monomer shown in Table 1 (1-12) (60 parts), methyl methacrylate (2-1) (40 parts) and

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36/43 azobisisobutyronitrile polymerization initiator (1) (0.8 part) was added in drops to the container, by stirring at 110 to 115 ° C in a nitrogen atmosphere. After the addition in drops, azobisisobutyronitrile (2) (0.5 part) was added to the resulting reaction solution, and then the reaction was carried out for 4 hours at 110 ° C, with stirring, in order to obtain a comparative copolymer [Q-3]. Table 2 shows the average molecular weight (Mw) and the non-volatile content of [Q-3].

Comparative Production Example 4 (Copolymer Production [Q-4]) [0105] A solvent (xylene) (300 parts) was loaded into a reaction vessel equipped with a thermometer, reflux condenser, stirrer and funnel. drip; then, a mixture of methyl methacrylate (140 parts), ethyl acrylate (40 parts), triisopropylsilyl acrylate (220 parts) and benzoyl peroxide (1) (2 parts) was added dropwise to the container stirring at around 100 ° C in a nitrogen atmosphere. After the addition in drops, benzoyl peroxide (2) (2 parts) was added to the resulting reaction solution and then the reaction was carried out for 4 hours at around 100 ° C, with stirring, in order to obtain a copolymer comparative [Q-4]. Table 4 shows the non-volatile content of [Q-4].

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Table 4 Comparative Production Example 4 Copolymer No. Q-4 Solvent 1 Xylene Butyl Acetate 300 For lonomer Triisopropylsilyl acrylate Methyl Methacrylate Ethyl Acrylate 220 140 40 Polymerization Initiator Benzoyl peroxide 2 Polymerization Initiator Benzoyl peroxide 2 Solvent 2 Xylene 100 Reaction Temperature ( ^D C) 100 Solid Content (%> 49.9

Comparative Examples 1 and 2 (Production of Coating Compositions) [0106] Copolymers [Q-2] and [Q-3], antifouling [B], release modifier [C], plasticizer [D] , the pigment, the anti-slip agent and the solvent were added to a container in the proportion (% by weight) shown in Table 3; then, glass beads with a diameter of 1.5 to 2.5 mm were added for mixing and dispersing, and the resulting mixture was agitated, mixed and dispersed by using the stirrer of the experiment, in order to prepare comparative film compositions of coating [Hl] and [H-2]. In Table 3, the release modifier [C] is a solution obtained by dissolving gum pitch in the same solvent used for the production of the comparative copolymer (the amount of gum pitch in the solution is 50% by weight).

Comparative Examples 3 and 4 (Production of the Compositions of

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Coating) [0107] The copolymer [Q-4] and the components shown in Table 5 were added to a container in the proportion (% by weight) shown in Table 5; then, glass beads with a diameter of 1.5 to 2.5 mm were added for mixing and dispersing, and the resulting mixture was stirred, mixed and dispersed using the stirrer of the experiment, in order to prepare the comparative film compositions coating [H-3] and [H-4].

Table 5 Ex. Comp. H-3 H-4 Comparative Copolymer Q-4 35 35 Cuprous Oxide (Anti-fouling) 40 40 Zinc Oxide (Pigment) 5 5 Red Iron Oxide (Pigment) 2 2 Talc (Pigment) 3 3 2,4,5,6-Tetrachloroisophthalonitrile (Antifouling) 5 5 Dispalon4300 (Dispersant) 0.5 0.5 Tetraethoxysilane (Dehydrating Agent) 1 0 Xylene (Solvent) 10 10 Total 101.5 100.5

Test Example 1 (Storage Stability Test) [0108] Each of the coating compositions obtained in Examples 1 to 18 and Comparative Examples 1 to 4 was sealed in a 100 ml wide-mouthed tin can and stored in a incubator at 50 ° C for two months, after that time, the viscosity of the coating composition was measured. Viscosity was measured using a viscometer

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Brookfield at 25 ° C.

[0109] The results are shown in Table 6.

iTabela6 Storage Stability Test

1 Start Viscosity 'bait after Storage for 2 months at 50 ^: ij _ (mPa-s) Viscosity (mPa-s) Increase in Viscosity I Ex. 1 820 850 30 I 2 1750 1780 30 i 3 1460 1480 20 | 4 620 620 Hi 5 600 600 ⁰ I 6 700 710 10 i 7 720 720 ......................................O........... .......................... I s 540 540 0 I 9 610 620 ίο I 10 690 690 ......................................O........... ..........................! 11 640 640 ......................................O........... ........................... I 12 620 620 O ! 13 570 560 -ίο I 14 530 530 ......................................O........... ..........................! 15 560 570 16 480 480 O ! 17 570 580 ίο I 18 530 530 ίο i i ». Comp. H-1 1920 1940 20 I H-2 460 460 O ! H-3 650 720 70 l H-4 640 Freezing Freezing |

Test Example 2 (Solubility Test for Coating Films) [0110] A tank was provided with a rotating drum 318 mm in diameter and 440 mm high in its center, in order to allow the rotation of the drum by means of a motor. The tank was also provided with a heating and cooling device to keep the seawater temperature constant and an automatic pH controller to keep the seawater pH constant.

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40/43 [0111] The test plates were prepared according to the following method.

[0112] Each of the antifouling coating compositions obtained in Examples 1 to 18 and in Comparative Examples 1 to 3 was applied to an anticorrosive coating film on a hard vinyl chloride plate (75 x 150 x 1 mm), so that the thickness after drying was about 100 pm. The applied coating was dried for one day at 40 ° C, thereby preparing a test plate having a dry coating film with a thickness of about 100 pm.

[0113] The test plate prepared in this way was fixed to the rotating drum of the rotating apparatus mentioned above to come into contact with sea water, and the rotating drum was rotated at a speed of 37 km / h for 12 months. During the test, the sea water temperature was maintained at 25 ° C and the pH, at 8.0 to 8.2; sea water was replaced once a week.

[0114] After testing started, every three months, the initial thickness of the coating film and the remaining thickness of the coating film were measured for each test plate using a microscope, and the thickness of the dissolved coating film was calculated from the difference between thicknesses to provide the dissolved amount of the coating film.

[0115] The results are shown in Table 7.

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Solubility Test for Coating Films Consumed Coating Film Thickness (pm) iTabela 7 ι ι

ι j ι ι

1 1 1 1 1 1 1 1 1 3 months 6 months 9 months 12 months Monthly Average of | Film thickness | Coating Consumed I after 12 Months | 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 ι 1 15 28 45 53 4.4 2 13 26 43 60 ....................................... 5.0 .......... .............................. | 3 16 30 48 64 5.3 | 4 11 20 29 35 2.9 I 5 9 18 27 35 2.9 | 6 12 20 30 40 3.3 I 7 9 16 25 32 2 7 I ....................................... I 8 8 16 26 35 2.9 | 9 10 22 29 37 ΖΖΖΖΖΖΖΣΖΖΖΖΖΖ 10 11 20 32 43 3.6 I 11 13 22 34 43 ....................................... 3,6 ........ ................................. | 12 17 30 43 52 4.3 I 13 12 22 33 47 ....................................... 3.9 ........ ................................. | 14 14 26 38 48 ....................................... 4.0 .......... ..............................1 15 13 27 38 49 4 1 I ....................................... 7.? ........ ...................................... ι 16 18 33 46 60 ....................................... 5.0 .......... ..............................1 17 12 26 32 45 3.8 ι 18 10 22 30 40 3.3 I Ex. | Comp. H-1 6 10 9 10 ....................................... P.8 ........ .................................1 H-2 20 35 45 48 4.0 ι H-3 14.0 35 45 62 5.2 |

Test Example 3 (Anti-fouling Test) [0116] Each of the coating compositions obtained in Examples 1 to 18 and Comparative Examples 1 to 3 was applied to both surfaces of a hard vinyl chloride plate (100 x 200 x 2 mm), so that the thickness of the dry coating film was about 200 pm. The applied coating was dried for one day at 40 ° C in order to prepare a test plate having a dry coating film with a thickness of about 200 µm. This test plate was immersed 1.5 m below sea level in Owase City, Mie Prefecture, Japan, and the inlay on the test plate

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42/43 were examined for 18 months.

[0117] The results are shown in Table 8.

[0118] Note that the numbers in Table 8 represent the areas (%) where the fouling organisms have settled.

ι | Table 8

Anti-fouling test

1 1 1 1 Area Occupied by Bodies the (%) I Description of Incrustation 3 months 6 months 9 months 12 months 18 months 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 0 0 0 0 0 Jenhuma (mud only) 2 0 0 0 0 0 Jenhuma (mud only) 3 0 0 0 0 0 'Jenhuma (mud only) 4 0 0 0 0 0 Jenhuma (mud only) 5 0 0 0 0 0 Jenhuma (mud only) 6 0 0 0 0 0 Jenhuma (mud only) 7 0 0 0 0 0 Jenhuma (mud only) 8 0 0 0 0 0 Jenhuma (mud only) 9 0 0 0 0 0 Jenhuma (mud only) 10 0 0 0 0 0 Jenhuma (mud only) 11 0 0 0 0 0 Jenhuma (mud only) 12 0 0 0 0 0 Jenhuma (mud only) 13 0 0 0 0 0 Jenhuma (mud only) 14 0 0 0 0 0 Jenhuma (mud only) 15 0 0 0 0 0 Jenhuma (mud only) 16 0 0 0 0 0 Jenhuma (mud only) 17 0 0 0 0 0 Jenhuma (mud only) 18 0 0 0 0 0 Jenhuma (mud only) EX. | Comp. 1 H-1 10 30 90 Test Interruption Barnacles, Serpula, | Ascidia | H-2 0 0 0 0 10 Serpula | H-3 0 0 0 0 10 Serpula |

Test Example 4 (Physical Properties Test of Coating Films) [0119] The test plate used in Test Example 2 (Solubility Test for Coating Films) was subjected to the test during the rotation of the rotating drum for 18 months in same conditions as in Test Example 2. The condition of the respective coating films of Examples 1 to 18 and Comparative Examples 1 to 3 was observed after 6 months, 12 months and 18 months from the start of the test.

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Assessment of Physical Properties of Coating Films A: Swelling, blistering, cracking, peeling, or the like, are not seen in the coating film and there has been no change since the test began.

B: Swelling, blistering, cracking, peeling, or the like, are not seen in the coating film.

C: Swelling, blistering, cracking, peeling, or the like, are slightly observed in the coating film.

D: Swelling, blistering, cracking, peeling, or the like, are apparent in the coating film.

[0120] The results are shown in Table 9.

Table 9 [Table 9 ι

Physical Properties Test I Coating Film Status | 6 months 12 months 18 months i Ex. 1 THE THE THERE 2 THE THE THE 3 THE THE THERE 4 THE THE THERE 5 THE THE THERE 6 THE THE ...............................and.................. ............ ί 7 THE THE THERE 8 THE THE .............................. λ ................... ........... | 9 THE THE ...............................and.................. ............. 10 THE THE THE 11 THE THE ^A ! 12 THE B C: Irregular Surface | 13 THE THE THERE 14 THE THE THE 15 THE THE THERE 16 B C: Irregular Surface C: Crack | 17 THE THE ^A I 18 THE THE THE Comp. Ex. H-1 THE B ...............................B.................. ............. H-2 D: Bubble D: Bubble, Crack D: Stripping | H-3 THE B B ι

Petition 870180071999, of 8/16/2018, p. 55/59

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Claims (11)

1. COMPOSITION OF ANTI-SCALING COATING that contains a copolymer [A] obtained by copolymerizing a monomer represented by the general formula (1): (1) characterized by the fact that X represents acryloyloxy, methacryloyloxy, crotonoyloxy or isocrotonoyloxy, R ¹ represents a hydrogen or methyl atom and R ² represents an alkyl group containing from one to six carbons; and a polymerizable monomer represented by the general formula (2) (2) where R ³ represents a hydrogen or methyl atom, R ⁴ represents an alkyl group containing one to ten carbons, or an alkyl group containing two to five carbons , to which an alkoxy group containing from one to four carbons is attached. 2. COMPOSITION OF ANTI-FLOOD COATING according to claim 1, characterized by the fact that when R ² in the general formula (1) is an alkyl group containing one or two carbons, R ⁴ in the general formula (2) is a branched alkyl group containing three to ten carbons. 3. COMPOSITION OF ANTI-FLOOD COATING according to claim 2, characterized by the fact that when R ² in the general formula (1) is an alkyl group containing one or two carbons, the polymerizable monomer (2) is isobutyl acrylate or isobutyl methacrylate. Petition 870180071999, of 8/16/2018, p. 56/59 2/3 4. ANTI-FLOOD COATING COMPOSITION according to claim 1, characterized by the fact that when R ² in the general formula (1) is an alkyl group containing three to six carbons, the alkyl group is a branched alkyl group. 5. COMPOSITION OF ANTI-FLOOD COATING according to any one of claims 1 to 4, characterized by the fact that the amount of use of the monomer (1) is 10 to 80% by weight in relation to the total weight of the monomers. 6. COMPOSITION OF ANTI-FLOOD COATING according to any one of claims 1 to 5, characterized by the fact that the amount of use of the monomer (2) is 20 to 90% by weight in relation to the total weight of the monomers. 7. COMPOSITION OF ANTI-FLOOD COATING according to any one of claims 1 to 6, characterized by the fact that it comprises an antifouling [B] which is a cuprous oxide. 8. COMPOSITION OF ANTI-FLOOD COATING according to any one of claims 1 to 7, characterized by the fact that it comprises a release modifier [C] that is at least one member selected from the group consisting of pitch, derived from pitch and salt of the pitch metal. 9. ANTI-SCALING TREATMENT METHOD characterized by the fact that it comprises the step of forming an anti-fouling coating film on the surface of an object to be coated using the anti-fouling coating composition according to any of the claims 1 to 8. 10. ANTI-FLOOD COATING FILM characterized by the fact that it is formed by the use of the composition Petition 870180071999, of 8/16/2018, p. 57/59 3/3 anti-fouling coating according to any one of claims 1 to 8. 11. COATED OBJECT characterized by the fact that it has the anti-fouling coating film of claim 10 on its surface. Petition 870180071999, of 8/16/2018, p. 58/59